WO1992007060A1 - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
WO1992007060A1
WO1992007060A1 PCT/EP1991/001989 EP9101989W WO9207060A1 WO 1992007060 A1 WO1992007060 A1 WO 1992007060A1 EP 9101989 W EP9101989 W EP 9101989W WO 9207060 A1 WO9207060 A1 WO 9207060A1
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WO
WIPO (PCT)
Prior art keywords
base composition
detergent
nonionic surfactant
detergent base
composition
Prior art date
Application number
PCT/EP1991/001989
Other languages
French (fr)
Inventor
William Derek Emery
Original Assignee
Unilever N.V.
Unilever Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever N.V., Unilever Plc filed Critical Unilever N.V.
Publication of WO1992007060A1 publication Critical patent/WO1992007060A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to a granular
  • spray-dried detergent base composition suitable for use in detergent compositions having a surfactant system consisting essentially of fatty acid soap and nonionic surfactant, and a detergency builder system based on aluminosilicate.
  • the composition of the invention shows an exceptionally high absorptivity for liquid nonionic surfactants, and flow properties are excellent.
  • Nonionic surfactants having a low average degree of ethoxylation these materials are liquid at ambient temperature, and unsuitable for processing through spray-drying towers.
  • Conventional spray-dried base powders containing non-soap anionic surfactant (for example, alkylbenzene sulphonate or primary alcohol sulphate), and low levels of nonionic surfactant are relatively porous and are capable of taking up quite large amounts of sprayed-on nonionic surfactant while retaining satisfactory powder properties (flow, compressibility, resistance to caking). Small percentages of soap, for example, 1 wt%, as in the well-known "ternary active" powders, can be accommodated without problems.
  • electrolytes sodium carbonate, sodium sulphate
  • low-salt or salt-free base powders can take up large amounts of liquid nonionic surfactant without detriment to powder properties, and can therefore be used to formulate detergent powders based on a soap/nonionic surfactant surfactant system that combine good detergency performance and excellent powder properties.
  • EP 344 629A (Henkel) discloses a granular
  • composition comprising aluminosilicate (45-75 wt%), a small amount of fatty acid soap (1-6 wt%), acrylic and/or maleic polymer (1-12 wt%), optionally plus sodium
  • nonionic surfactant a small amount (up to 5 wt%) of nonionic surfactant.
  • the granular material 65-90 wt%) may be used as a carrier for nonionic surfactant (10-35 wt%).
  • No. 89 24294.5 (Case C.3341) filed on 27 October 1989 discloses spray-dried granular detergent compositions having a soap/nonionic surfactant system and built with relatively high levels of alkali metal aluminosilicate.
  • No. 90 12613.7 (Case C.3373) discloses spray-dried soap powders containing soap (high levels), non-soap anionic surfactant, sodium carbonate, sodium silicate and minor ingredients.
  • EP 270 240A (Unilever Case C.3144) discloses
  • compositions free of sodium carbonate, and containing primary alcohol sulphate, alkylbenzene sulphonate, nonionic surfactant, and small amounts of soap are containing primary alcohol sulphate, alkylbenzene sulphonate, nonionic surfactant, and small amounts of soap.
  • the present invention provides a granular
  • spray-dried detergent base composition which comprises:
  • an organic surfactant system consisting essentially of from 7 to 40 wt% of fatty acid soap
  • the invention also provides a granular detergent composition which comprises
  • ingredients to 100 wt%. all percentages being based on the granular detergent composition.
  • the first subject of the present invention is a granular detergent base composition, prepared by
  • the detergent base composition contains aluminosilicate builder (in a substantial amount) and soap (in a substantial amount).
  • the organic surfactant system also includes a nonionic surfactant, more preferably in a minor amount, suitably from 1 to 12 wt% (on the base composition).
  • the nonionic surfactant is preferably an alkoxylated nonionic surfactant.
  • the detergency builder system may advantageously include an organic sequestrant builder in addition to the alkali metal aluminosilicate. This is preferably present in an amount of from 2 to 30 wt%.
  • the detergent base composition of the invention is preferably substantially free of sodium carbonate and sodium sulphate.
  • the resulting composition may then be admixed with other, separately prepared ingredients to form a more fully formulated final composition.
  • This is the second subject of the present invention.
  • the alkalinity that is lost by restricting sodium carbonate in the base powder, or excluding it altogether may be replaced by admixing (postdosing) solid sodium carbonate, for example, as granular soda ash.
  • compositions of the invention are also non-base ingredients.
  • Other non-base ingredients may also be present, as discussed below.
  • Preferred compositions of the invention are
  • compositions of the invention are preferably free of phosphate builders. Efficient detergency building is provided by alkali metal aluminosilicate, in a relatively large amount, assisted by an organic sequestrant which is preferably an water-soluble, preferably alkali metal, salt of citric acid or of an acrylic or acrylic/maleic polymer.
  • the base composition of the invention contains from 7 to 40 wt%, preferably from 10 to 40 wt%, more
  • the soap provides detergency, detergency building and foam control.
  • This total will generally be a blend composed of soaps of different chain lengths, and of saturated and unsaturated soaps.
  • Commercially available soaps suitable for use in the present invention include those derived from hardened or natural tallow, coconut oil, rapeseed oil, and mixtures of these. It is also possible, however, to manipulate the chain length distribution and the amount of unsaturation so as to maximise the efficiency of the final blend as surfactant and (to a lesser extent) as builder, while giving also giving optimum stability, and dissolution and dispersion properties.
  • the soap may advantageously contain at least 40 wt% unsaturated soap. This is preferably in the form of oleate (singly unsaturated soap) rather than linoleate (doubly unsaturated soap) because the latter material can have a tendency to rancidity.
  • composition is intended particularly for use in low-temperature washing, a soap blend is
  • GB 2 034 741B (Unilever) discloses a soap blend having a low Krafft temperature (below 25°C), derived from a C 12-22 fatty acid mixture comprising
  • composition of the invention derived from tallow and coconut, contains 14 wt% C 12 saturated soap, 40 wt% C 18 saturated soap, and 46 wt% C 18 unsaturated soap (oleate).
  • This blend has a Krafft point of about 45°C and exhibits excellent dispersion, dissolution and detergency in the 60°C wash cycle.
  • the optional nonionic surfactant is selected from the group consisting of:
  • the base composition of the invention may also contain from 1 to 12 wt%, preferably from 5 to 8 wt%, of nonionic surfactant, preferably alkoxylated nonionic surfactant.
  • Nonionic surfactants are well known to those skilled in the art, and include the C 12-20 primary and secondary aliphatic alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
  • any lower-ethoxylated nonionic surfactant to be included in the final composition is preferably sprayed-on rather than included in the base composition.
  • the amount of nonionic surfactant permitted in the base composition is limited to 1 to 12 wt%, but in the expectation that the final detergent composition of which the base composition will form part will contain
  • nonionic surfactant sprayed on to the base composition.
  • the amount of sprayed-on nonionic surfactant sprayed on to the base composition.
  • surfactant in the final composition is suitably from 1 to 35 wt%, more preferably from 1 to 20 wt%.
  • the sprayed-on nonionic surfactant suitably has a degree of ethoxylation within the range of from 3 to 8 moles of ethylene oxide per mole of alcohol.
  • the alkali metal aluminosilicate The principal detergency builder of the base
  • composition of the invention is alkali metal
  • aluminosilicate present in an amount of from 28 to 80 wt%, preferably 4.0 to 60 wt%, more preferably from 46 to 60 wt%, calculated on an anhydrous basis, on the base composition.
  • the alkali metal (preferably sodium) aluminosilicate builder may be crystalline or amorphous or a mixture thereof, and has the general formula
  • aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above) and have a particle size of not more than about 100 ⁇ m, preferably not more than about 20 ⁇ m. Both amorphous and crystalline aluminosilicates can be made readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • Crystalline aluminosilicates (zeolites) are
  • Suitable materials are described, for example, in GB 1 473 201 (Henkel) and GB 1 429 143 (Procter & Gamble).
  • the preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
  • Especially preferred for use in the present invention is Type 4A zeolite.
  • EP 384 070A (Unilever) published on 29 August 1990 may also be used in the base composition of the invention.
  • the aluminosilicate is preferably assisted by an organic sequestrant cobuilder, more preferably a material free of nitrogen or phosphorus, suitably present in an amount of from 2 to 30 wt%, preferably from 5 to 20 wt%, calculated on the base composition.
  • an organic sequestrant cobuilder more preferably a material free of nitrogen or phosphorus, suitably present in an amount of from 2 to 30 wt%, preferably from 5 to 20 wt%, calculated on the base composition.
  • the organic builder is preferably a water-soluble salt of a polycarboxylic acid, for example, alkali metal (preferably sodium) oxydisuccinate, tartrate
  • carboxymethyloxysuccinate polyacetal carboxylate, or, most preferably, citrate.
  • Water-soluble salts (preferably alkali metal) salts of non-polymeric polycarboxylic acids, especially citric acid, are especially preferred. Most preferably, sodium citrate is used in an amount of from 5 to 20 wt%.
  • Water-soluble salts of polymeric polycarboxylic acids are also effective cobuilders for use in the compositions of the invention and are also suitably used in amounts of from 5 to 20 wt%.
  • Sodium carbonate is also effective cobuilders for use in the compositions of the invention and are also suitably used in amounts of from 5 to 20 wt%.
  • the base composition of the invention contains not more than 5 wt% of sodium carbonate and sodium sulphate, and is preferably substantially free of both sodium sulphate and sodium carbonate.
  • the final composition thus preferably contains postdosed sodium carbonate, suitably in an amount of up to 25 wt%, for example, from 2 to 25 wt%, preferably from 5 to 15 wt%.
  • Sodium carbonate may be postdosed in any suitable solid form, for example, light soda ash, heavy soda ash or, preferably, granular soda ash.
  • a low level of water-soluble alkali metal silicate preferably sodium silicate - desirably not more than 10 wt% - may be included in the base composition of the invention, in order to provide
  • the base composition of the invention may also contain other conventional minor ingredients, for example
  • fluorescers examples include fluorescers, and antiredeposition agents such as sodium carboxymethylcellulose.
  • antiredeposition agents such as sodium carboxymethylcellulose.
  • the base composition of the invention may suitable constitute from 30 to 99 wt%, preferably from 50 to 97 wt%, of the final composition.
  • ingredients that may be admixed include peroxy bleach systems, proteolytic enzymes, lipolytic enzymes, amylolytic enzymes, fabric softening granules, and perfumes.
  • a suitable peroxy bleach system consists of an inorganic persalt, for example, sodium perborate
  • tetrahydrate, sodium perborate monohydrate or sodium percarbonate in combination with a bleach precursor, for example, tetraacetylethylenediamine (TAED).
  • TAED tetraacetylethylenediamine
  • a bleach stabiliser dashed metal sequestrant
  • the peroxy bleach, system is suitably present in an amount of from 5 to 30 wt%, preferably from 5 to 15 wt%.
  • Preferred fabric softening granules are those comprising clay and nonionic surfactant in a weight ratio of from 2:3 to 20:1, as described and claimed in
  • EP 287 343A and EP 287 344A (Unilever). These are suitably present in an amount such that the amount of clay in the final composition is within the range of from 1.5 to 35 wt%, preferably from 4 to 15 wt%, the nonionic surfactant specifically associated with the clay being accounted for within the total amount of nonionic surfactant already specified.
  • the detergent base composition and final composition of the invention may be prepared to any desired bulk density.
  • the base composition of the invention may be subjected to a granulation/densification process as described and claimed in our aforementioned copending British Patent Application No. 89 24294.5 (Case C.3341).
  • the base composition is densified in a high-speed mixer/granulator. Densification will normally be carried out after spray-on of the nonionic surfactant, but alternatively the nonionic surfactant may be sprayed into the high-speed mixer/granulator during the densification process. Postdosed ingredients, such as sodium carbonate, are added after densification is complete.
  • the soap blend used was the sodium salt of a fatty acid mix composed of 14 wt% lauric acid, 40 wt% stearic acid and 46 wt% oleic acid.
  • nonionic surfactants used were Synperonic (Trade Mark) A7 and A3 ex ICI, both based on C 12-15 primary alcohol and containing respectively an average of 7 and 3 moles of ethylene oxide per mole of alcohol.
  • the polymer used in Examples 5 to 7 was Sokalan (Trade Mark) CP5 ex BASF, an acrylic/maleic copolymer in sodium salt form.
  • the granular base compositions were prepared by spray-drying aqueous slurries. 3E0 nonionic surfactant was sprayed on subsequently. Postdosed sodium carbonate was in the form of granular soda ash. Compositions and powder properties are shown in the

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Abstract

A granular spray-dried detergent base composition is provided which exhibits a high porosity and can take up large amounts of nonionic surfactant material while maintaining good powder properties. This base composition comprises: (i) an organic surfactant system consisting essentially of from 7 to 40 wt. % of fatty acid soap, (ii) a detergency builder system consisting essentially of from 28 to 80 wt. % (anhydrous basis) of crystalline or amorphous alkali metal aluminosilicate, (iii) optionally other detergent ingredients, and moisture to 100 wt. %, the base composition containing not more than 5 wt. % of sodium carbonate and sodium sulphate, all percentages being calculated on the base composition.

Description

DETERGENT COMPOSITIONS
TECHNICAL FIELD
The present invention relates to a granular
spray-dried detergent base composition suitable for use in detergent compositions having a surfactant system consisting essentially of fatty acid soap and nonionic surfactant, and a detergency builder system based on aluminosilicate. The composition of the invention shows an exceptionally high absorptivity for liquid nonionic surfactants, and flow properties are excellent.
BACKGROUND Spraying of liquid nonionic surfactants onto a spray-dried detergent base powder is now an established manufacturing technique which has become especially prevalent in recent years with the increasing use of nonionic surfactants having a low average degree of ethoxylation: these materials are liquid at ambient temperature, and unsuitable for processing through spray-drying towers. Conventional spray-dried base powders containing non-soap anionic surfactant (for example, alkylbenzene sulphonate or primary alcohol sulphate), and low levels of nonionic surfactant are relatively porous and are capable of taking up quite large amounts of sprayed-on nonionic surfactant while retaining satisfactory powder properties (flow, compressibility, resistance to caking). Small percentages of soap, for example, 1 wt%, as in the well-known "ternary active" powders, can be accommodated without problems.
However, base powders containing more substantial quantities of soap have always been found to be less porous and to take up much lower levels of liquid
nonionic surfactant before powder properties deteriorate. This experience has been gained with powders of high ionic strength, built with sodium tripolyphosphate; and also with powders built with insoluble aluminosilicates but containing conventional levels of soluble
electrolytes (sodium carbonate, sodium sulphate).
It has now been found that spray-dried detergent base powders containing substantial amounts of soap and built with insoluble aluminosilicate exhibit
significantly higher porosity if levels of inorganic water-soluble electrolytes such as sodium carbonate and sodium sulphate are severely restricted, or preferably substantially zero. These low-salt or salt-free base powders can take up large amounts of liquid nonionic surfactant without detriment to powder properties, and can therefore be used to formulate detergent powders based on a soap/nonionic surfactant surfactant system that combine good detergency performance and excellent powder properties. PRIOR ART
EP 344 629A (Henkel) discloses a granular
composition comprising aluminosilicate (45-75 wt%), a small amount of fatty acid soap (1-6 wt%), acrylic and/or maleic polymer (1-12 wt%), optionally plus sodium
sulphate and a small amount (up to 5 wt%) of nonionic surfactant. The granular material (65-90 wt%) may be used as a carrier for nonionic surfactant (10-35 wt%).
Our copending British Patent Application
No. 89 24294.5 (Case C.3341) filed on 27 October 1989 discloses spray-dried granular detergent compositions having a soap/nonionic surfactant system and built with relatively high levels of alkali metal aluminosilicate.
Our copending British Patent Application
No. 90 12613.7 (Case C.3373) discloses spray-dried soap powders containing soap (high levels), non-soap anionic surfactant, sodium carbonate, sodium silicate and minor ingredients.
EP 270 240A (Unilever Case C.3144) discloses
spray-dried detergent base powders free of electrolyte, containing non-soap anionic surfactant, optional nonionic surfactant, optionally low levels of soap,
aluminosilicate builder and polymeric polycarboxylate.
Our copending British Patent Application
No. 90 12612.9 filed on 6 June 1990 (Case C.3372)
discloses spray-dried granular detergent base
compositions free of sodium carbonate, and containing primary alcohol sulphate, alkylbenzene sulphonate, nonionic surfactant, and small amounts of soap. DEFINITION OF THE INVENTION
The present invention provides a granular
spray-dried detergent base composition which comprises:
(i) an organic surfactant system consisting essentially of from 7 to 40 wt% of fatty acid soap,
(ii) a detergency builder system consisting
essentially of from 28 to 80 wt% (anhydrous basis) of crystalline or amorphous alkali metal
aluminosilicate,
(iii) optionally other detergent ingredients, and moisture to 100 wt%, the base composition containing not more than 5 wt% of sodium carbonate and sodium sulphate, all percentages being calculated on the base composition.
The invention also provides a granular detergent composition which comprises
(i) from 30 to 99 wt% of a spray-dried base composition as defined in the previous paragraph,
(ii) from 1 to 35 wt% of sprayed-on nonionic surfactant,
(iii) from 0 to 25 wt% admixed sodium carbonate.
(iv) optionally other compatible detergent
ingredients to 100 wt%. all percentages being based on the granular detergent composition.
DETAILED DESCRIPTION OF THE INVENTION
The first subject of the present invention is a granular detergent base composition, prepared by
spray-drying an aqueous slurry. The detergent base composition contains aluminosilicate builder (in a substantial amount) and soap (in a substantial amount).
Preferably the organic surfactant system also includes a nonionic surfactant, more preferably in a minor amount, suitably from 1 to 12 wt% (on the base composition). The nonionic surfactant is preferably an alkoxylated nonionic surfactant.
The detergency builder system may advantageously include an organic sequestrant builder in addition to the alkali metal aluminosilicate. This is preferably present in an amount of from 2 to 30 wt%.
The detergent base composition of the invention is preferably substantially free of sodium carbonate and sodium sulphate.
While the detergent base composition of the
invention could in principle be used as a detergent powder in its own right, it is intended that it should be used in conjunction with additional nonionic surfactant that is sprayed on.
If desired, the resulting composition may then be admixed with other, separately prepared ingredients to form a more fully formulated final composition. This is the second subject of the present invention. In particular, the alkalinity that is lost by restricting sodium carbonate in the base powder, or excluding it altogether, may be replaced by admixing (postdosing) solid sodium carbonate, for example, as granular soda ash.
Other non-base ingredients may also be present, as discussed below. Preferred compositions of the invention are
substantially free of non-soap anionic surfactants, and yet exhibit cleaning performance comparatble with that of conventional detergent powders on the market today based on sulphonate- or sulphate-type anionic detergents.
Compositions of the invention are preferably free of phosphate builders. Efficient detergency building is provided by alkali metal aluminosilicate, in a relatively large amount, assisted by an organic sequestrant which is preferably an water-soluble, preferably alkali metal, salt of citric acid or of an acrylic or acrylic/maleic polymer.
The fatty acid soap
The base composition of the invention contains from 7 to 40 wt%, preferably from 10 to 40 wt%, more
preferably from 10 to 30 wt%, of fatty acid soap. The soap provides detergency, detergency building and foam control.
This total will generally be a blend composed of soaps of different chain lengths, and of saturated and unsaturated soaps. Commercially available soaps suitable for use in the present invention include those derived from hardened or natural tallow, coconut oil, rapeseed oil, and mixtures of these. It is also possible, however, to manipulate the chain length distribution and the amount of unsaturation so as to maximise the efficiency of the final blend as surfactant and (to a lesser extent) as builder, while giving also giving optimum stability, and dissolution and dispersion properties. The soap may advantageously contain at least 40 wt% unsaturated soap. This is preferably in the form of oleate (singly unsaturated soap) rather than linoleate (doubly unsaturated soap) because the latter material can have a tendency to rancidity.
If the composition is intended particularly for use in low-temperature washing, a soap blend is
advantageously chosen that has a Krafft point not higher than 50°C, so that optimum dispersion of the soap
throughout the wash liquor and dissolution during the wash cycle is ensured.
For example, GB 2 034 741B (Unilever) discloses a soap blend having a low Krafft temperature (below 25°C), derived from a C12-22 fatty acid mixture comprising
(i) from 5 to 60 wt% of one of more saturated or unsaturated fatty acids having 14 or fewer carbon atoms,
(ii) from 5 to 32 wt% of one or more saturated fatty acids having more than 14 carbon atoms ,
(iii) from 35 to 90 wt% of one mor more unsaturated fatty acids having 14 or more carbon atoms. One soap blend suitable for use in the base
composition of the invention, derived from tallow and coconut, contains 14 wt% C12 saturated soap, 40 wt% C18 saturated soap, and 46 wt% C18 unsaturated soap (oleate). This blend has a Krafft point of about 45°C and exhibits excellent dispersion, dissolution and detergency in the 60°C wash cycle. Another blend, especially suitable for very low temperature washing, contains a higher
proportion of short-chain saturated soap (39 wt%), and a lower proportion of longer-chain saturated soap (15 wt%), and has a Krafft point of about 12°C.
The optional nonionic surfactant
The base composition of the invention may also contain from 1 to 12 wt%, preferably from 5 to 8 wt%, of nonionic surfactant, preferably alkoxylated nonionic surfactant.
Nonionic surfactants are well known to those skilled in the art, and include the C12-20 primary and secondary aliphatic alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
Especially preferred for use in the base composition of the invention are those with degrees of ethoxylation of from 6 to 12 moles of ethylene oxide per mole of alcohol: any lower-ethoxylated nonionic surfactant to be included in the final composition is preferably sprayed-on rather than included in the base composition.
The amount of nonionic surfactant permitted in the base composition is limited to 1 to 12 wt%, but in the expectation that the final detergent composition of which the base composition will form part will contain
additional nonionic surfactant sprayed on to the base composition. The amount of sprayed-on nonionic
surfactant in the final composition, as previously indicated, is suitably from 1 to 35 wt%, more preferably from 1 to 20 wt%. The sprayed-on nonionic surfactant suitably has a degree of ethoxylation within the range of from 3 to 8 moles of ethylene oxide per mole of alcohol.
The alkali metal aluminosilicate The principal detergency builder of the base
composition of the invention is alkali metal
aluminosilicate, present in an amount of from 28 to 80 wt%, preferably 4.0 to 60 wt%, more preferably from 46 to 60 wt%, calculated on an anhydrous basis, on the base composition.
The alkali metal (preferably sodium) aluminosilicate builder may be crystalline or amorphous or a mixture thereof, and has the general formula
0.8-1.5 Na2O.Al2O3.0.8-6 SiO2.
These materials contain some bound water and are required to have a calcium ion exchange capacity of at least about 50 mg CaO/g. The preferred aluminosilicates contain 1.5-3.5 SiO2 units (in the formula above) and have a particle size of not more than about 100 μm, preferably not more than about 20 μm. Both amorphous and crystalline aluminosilicates can be made readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Crystalline aluminosilicates (zeolites) are
preferred for use in the present invention. Suitable materials are described, for example, in GB 1 473 201 (Henkel) and GB 1 429 143 (Procter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof. Especially preferred for use in the present invention is Type 4A zeolite.
The novel zeolite P described and claimed in
EP 384 070A (Unilever) published on 29 August 1990 may also be used in the base composition of the invention.
The optional organic sequestrant cobuilder
The aluminosilicate is preferably assisted by an organic sequestrant cobuilder, more preferably a material free of nitrogen or phosphorus, suitably present in an amount of from 2 to 30 wt%, preferably from 5 to 20 wt%, calculated on the base composition.
The organic builder is preferably a water-soluble salt of a polycarboxylic acid, for example, alkali metal (preferably sodium) oxydisuccinate, tartrate
monosuccinate, tartrate disuccinate,
carboxymethyloxysuccinate, polyacetal carboxylate, or, most preferably, citrate.
Water-soluble salts (preferably alkali metal) salts of non-polymeric polycarboxylic acids, especially citric acid, are especially preferred. Most preferably, sodium citrate is used in an amount of from 5 to 20 wt%.
Water-soluble salts of polymeric polycarboxylic acids, especially acrylic, maleic and acrylic/maleic polymers, are also effective cobuilders for use in the compositions of the invention and are also suitably used in amounts of from 5 to 20 wt%. Sodium carbonate
The base composition of the invention contains not more than 5 wt% of sodium carbonate and sodium sulphate, and is preferably substantially free of both sodium sulphate and sodium carbonate.
However, as previously indicated, the presence of sodium carbonate in the final composition may be
advantageous in order to provide alkalinity in the wash. The final composition thus preferably contains postdosed sodium carbonate, suitably in an amount of up to 25 wt%, for example, from 2 to 25 wt%, preferably from 5 to 15 wt%.
Sodium carbonate may be postdosed in any suitable solid form, for example, light soda ash, heavy soda ash or, preferably, granular soda ash.
Optional base ingredients
If desired, a low level of water-soluble alkali metal silicate, preferably sodium silicate - desirably not more than 10 wt% - may be included in the base composition of the invention, in order to provide
protection against corrosion of metal washing machine parts, to increase alkalinity, and to provide powder structure.
The base composition of the invention may also contain other conventional minor ingredients, for
example, fluorescers, and antiredeposition agents such as sodium carboxymethylcellulose. The final detergent composition
As previously indicated, the base composition of the invention may suitable constitute from 30 to 99 wt%, preferably from 50 to 97 wt%, of the final composition.
The remainder of the final composition is
constituted by sprayed-on nonionic surfactant (1 to
30 wt% as previously indicated), preferably by postdosed sodium carbonate (0 to 25 wt% as previously indicated), and if desired by other compatible ingredients that provide additional performance benefits.
Examples of ingredients that may be admixed include peroxy bleach systems, proteolytic enzymes, lipolytic enzymes, amylolytic enzymes, fabric softening granules, and perfumes.
A suitable peroxy bleach system consists of an inorganic persalt, for example, sodium perborate
tetrahydrate, sodium perborate monohydrate or sodium percarbonate, in combination with a bleach precursor, for example, tetraacetylethylenediamine (TAED). If desired, a bleach stabiliser (heavy metal sequestrant) may also be present, although, as previously indicated, it may be preferred to avoid the use of sequestrants containing nitrogen or phosphorus. The peroxy bleach, system is suitably present in an amount of from 5 to 30 wt%, preferably from 5 to 15 wt%.
Preferred fabric softening granules are those comprising clay and nonionic surfactant in a weight ratio of from 2:3 to 20:1, as described and claimed in
EP 287 343A and EP 287 344A (Unilever). These are suitably present in an amount such that the amount of clay in the final composition is within the range of from 1.5 to 35 wt%, preferably from 4 to 15 wt%, the nonionic surfactant specifically associated with the clay being accounted for within the total amount of nonionic surfactant already specified.
Bulk density
The detergent base composition and final composition of the invention may be prepared to any desired bulk density.
If desired, the base composition of the invention may be subjected to a granulation/densification process as described and claimed in our aforementioned copending British Patent Application No. 89 24294.5 (Case C.3341). In the claimed process, the base composition is densified in a high-speed mixer/granulator. Densification will normally be carried out after spray-on of the nonionic surfactant, but alternatively the nonionic surfactant may be sprayed into the high-speed mixer/granulator during the densification process. Postdosed ingredients, such as sodium carbonate, are added after densification is complete.
Two processes suitable for densification of the base composition of the present invention are described respectively in EP 340 013A (Unilever Case C.3235) and EP 367 339A (Unilever Case C.7139). Examples
The invention will now be illustrated by the
following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated.
The soap blend used was the sodium salt of a fatty acid mix composed of 14 wt% lauric acid, 40 wt% stearic acid and 46 wt% oleic acid.
The nonionic surfactants used were Synperonic (Trade Mark) A7 and A3 ex ICI, both based on C12-15 primary alcohol and containing respectively an average of 7 and 3 moles of ethylene oxide per mole of alcohol.
The polymer used in Examples 5 to 7 was Sokalan (Trade Mark) CP5 ex BASF, an acrylic/maleic copolymer in sodium salt form. The granular base compositions were prepared by spray-drying aqueous slurries. 3E0 nonionic surfactant was sprayed on subsequently. Postdosed sodium carbonate was in the form of granular soda ash. Compositions and powder properties are shown in the
Tables which follow. Dynamic flow rates of 100 ml/s and above are good, figures above 110 ml/s being considered excellent. Compressibilities below 25 %v/v, after spray-on of nonionic surfactant, are preferred.
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001

Claims

1 A granular spray-dried detergent base composition which comprises:
(i) an organic surfactant system consisting essentially of from 7 to 40 wt% of fatty acid soap, (ii) a detergency builder system consisting
essentially of from 28 to 80 wt% (anhydrous basis) of crystalline or amorphous alkali metal
aluminosilicate, (iiI) optionally other detergent ingredients, and moisture to 100 wt%, the base composition containing not more than 5 wt% of sodium carbonate and sodium sulphate. all percentages being calculated on the base composition.
2 A detergent base composition as claimed in claim 1, which is substantially free of sodium carbonate and sodium sulphate.
3 A detergent base composition as claimed in claim 1 or claim 2, wherein the organic surfactant system (i) further comprises from 1 to 12 wt% of nonionic
surfactant. 4 A detergent base composition as claimed in claim 3, wherein the nonionic surfactant is an alkoxylated nonionic surfactant.
5 A detergent base composition as claimed in any preceding claim, which is substantially free of anionic non-soap surfactant.
6 A detergent base composition as claimed in any preceding claim, wherein the detergency builder system (ii) further comprises from 2 to 30 wt% of an organic sequestrant builder.
7 A detergent base composition as claimed in claim 6, wherein the organic sequestrant builder is a
water-soluble salt of citric acid.
8 A detergent base composition as claimed in claim 6, wherein the organic sequestrant builder is a
water-soluble salt of an acrylic or acrylic/maleic polymer.
9 A detergent base composition as claimed in any preceding claim, wherein the organic surfactant system comprises from 10 to 40 wt% of fatty acid soap. 10 A detergent base composition as claimed in claim 9, wherein the organic surfactant system comprises
from 10 to 30 wt% of fatty acid soap.
11 A detergent base composition as claimed in any preceding claim, wherein the detergency builder system comprises from 40 to 80 wt% (anhydrous basis) of alkali metal aluminosilicate.
12 A detergent base compsitiona as claimed in claim 11, wherein the detergency builder system comprises
from 46 to 80 wt% (anhydrous basis) of alkali metal aluminosilicate.
13 A granular detergent composition which comprises (i) from 30 to 99 wt% of a spray-dried base composition as defined in the previous paragraph,
(ii) from 1 to 35 wt% of sprayed-on nonionic surfactant.
(iii) from 0 to 25 wt% admixed sodium carbonate,
(iv) optionally other compatible detergent
ingredients to 100 wt%, all percentages being based on the granular detergent composition.
PCT/EP1991/001989 1990-10-18 1991-10-16 Detergent compositions WO1992007060A1 (en)

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GB9022660.6 1990-10-18

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998054286A1 (en) * 1997-05-30 1998-12-03 Unilever Plc Particulate detergent compositions
US6069124A (en) * 1997-05-30 2000-05-30 Lever Brothers Company Division Of Conopco, Inc. Granular detergent compositions and their production
WO2000039266A1 (en) * 1998-12-23 2000-07-06 Henkel Kommanditgesellschaft Auf Aktien Spray-dried granulated material
US6221831B1 (en) 1997-05-30 2001-04-24 Lever Brothers Company, Division Of Conopco, Inc. Free flowing detergent composition containing high levels of surfactant
US6303558B1 (en) 1997-05-30 2001-10-16 Lever Brothers Co., Division Of Conopco Detergent composition containing at least two granular components
WO2006010482A1 (en) * 2004-07-27 2006-02-02 Unilever Plc A particulate detergent composition, and packaging therefore

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0050894A1 (en) * 1980-10-29 1982-05-05 THE PROCTER & GAMBLE COMPANY Water-softening compositions on basis of aluminosilicates and detergent compositions containing them
EP0070192A1 (en) * 1981-07-15 1983-01-19 Unilever Plc Detergent additives and detergent compositions containing them
EP0165056A2 (en) * 1984-06-15 1985-12-18 Unilever N.V. Built detergent compositions
EP0344629A1 (en) * 1988-06-03 1989-12-06 Henkel Kommanditgesellschaft auf Aktien Granular adsorption material with improved flushing property
EP0425277A2 (en) * 1989-10-27 1991-05-02 Unilever Plc Detergent compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0050894A1 (en) * 1980-10-29 1982-05-05 THE PROCTER & GAMBLE COMPANY Water-softening compositions on basis of aluminosilicates and detergent compositions containing them
EP0070192A1 (en) * 1981-07-15 1983-01-19 Unilever Plc Detergent additives and detergent compositions containing them
EP0165056A2 (en) * 1984-06-15 1985-12-18 Unilever N.V. Built detergent compositions
EP0344629A1 (en) * 1988-06-03 1989-12-06 Henkel Kommanditgesellschaft auf Aktien Granular adsorption material with improved flushing property
EP0425277A2 (en) * 1989-10-27 1991-05-02 Unilever Plc Detergent compositions

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998054286A1 (en) * 1997-05-30 1998-12-03 Unilever Plc Particulate detergent compositions
US6069124A (en) * 1997-05-30 2000-05-30 Lever Brothers Company Division Of Conopco, Inc. Granular detergent compositions and their production
US6191095B1 (en) 1997-05-30 2001-02-20 Lever Brothers Company, A Division Of Conopco, Inc. Detergent compositions
US6221831B1 (en) 1997-05-30 2001-04-24 Lever Brothers Company, Division Of Conopco, Inc. Free flowing detergent composition containing high levels of surfactant
US6303558B1 (en) 1997-05-30 2001-10-16 Lever Brothers Co., Division Of Conopco Detergent composition containing at least two granular components
WO2000039266A1 (en) * 1998-12-23 2000-07-06 Henkel Kommanditgesellschaft Auf Aktien Spray-dried granulated material
WO2006010482A1 (en) * 2004-07-27 2006-02-02 Unilever Plc A particulate detergent composition, and packaging therefore

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